Yes, it can. It's usually, IIRC, emphatic and often contemptuous. If the prosecutor said, gesturing at the defendant, "She did it!" that might be a time for iste.

As far as the others are concerned, if you recall the "core" meanings of the pronouns (he, this [one], that [one]" but also remember that a literal translation will often be too much, you won't find it hard in practice.